Our invention is directed to a fragrance-emitting fiber useful in the creation of a controllably releasable or permanently fragrance-emitting dry or wet wipe laminar fabric article which optionally has efficacious antimicrobial properties. The article comprises a non-woven fabric lamina having woven therethrough and substantially throughout at least a finite portion of the laminar surface, such fragrance-imparting component-emitting fiber, which controllably and continuously releases fragrance and optionally (i) contains antimicrobial agent and/or (ii) at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance, at least for the time period of use of said dry or wet wipe laminar fabric article. Our invention is also directed to a process for the production of such fragrance-emitting fiber.
Fragranced fiber materials are well known in the prior art. Thus. U.S. Pat. No. 3,567,118 issued on Mar. 2, 1971 discloses composite fiber materials which are adapted for odorizing, deodorizing, sanitizing and cleansing purposes by treating the fibrous material with a coating of a hydrophilic acrylate or methacrylate containing an appropriate essence, bactericide, cleansing agent or the like. It is indicated in said U.S. Pat. No. 3,567,118 that both natural and synthetic fibers can be treated with a solution of the hydrophilic polymer, and that entrapment of the chemical agent can be prolonged by using a copolymer of the hydrophilic monomer with a minor amount of a hydrophobic monomer. U.S. Pat. No. 3,567,118 does not set forth the creation of a permanently, continuously fragrancing wet wipe or dry wipe. By the same token, U.S. Pat. No. 3,567,119 issued on Mar. 2, 1971 discloses methods for the incorporating of fragrance compounds or oil bouquets and/or topical antifungal or antibacterial agents, insect repellent compounds and certain odoriferous medicaments into polymeric or natural materials so that the fabricated product possesses the properties imparted by the additive or additives for a long period of time. Further, in U.S. Pat. No. 3,567,119, it is indicated that the efficiency of incorporating additives such as fragrance materials into the articles of the invention is improved by the use of surfactants and the effectiveness and duration of the additive or additives in the fabricated product is enhanced by employing antioxidants and/or ultraviolet radiation absorbers.
Additional perfumed fibers and antimicrobial product-containing fibers described by the prior art are as follows:
Japan Published Application No. 63/135573 published on Jun. 7, 1988 (perfumed fiber production by applying perfume emulsifier including spinning oil to fiber and heating in steam), assigned to Takasago Perfumery Company, Ltd.;
Japan Published Application No. 111/17174 published on May 27, 1999 discloses an antimicrobial fiber made up of polyester resin having a surface layer containing an antimicrobial agent. The antimicrobial agent consists of a quaternary phosphonium salt group which bonds ionically with an acid component of a hydrophilic resin (assigned to Toyobo KK); and
Japan Granted Patent No. 29/26446 published on Jul. 28, 1999 entitled xe2x80x9cDeodorizing Fibers, Manufacturing Method for the Fibers and Application Method for the Fibersxe2x80x9d assigned to Suzuki Sogyo KK.
Neither U.S. Pat. No. 3,567,118 nor U.S. Pat. No. 3,567,119 discloses the creation of fragrance-emitting fibers which can be used to form efficacious, continuous and permanent fragrance-emitting dry or wet wipe articles which have woven therethrough such fragrance-emitting fiber which is thermoplastic and substantially water-insoluble. Furthermore, none of the Japanese patent applications or granted patents disclose fibers which are fragrance-emitting and can be used to form fragrance-emitting dry or wet wipe articles which have woven therethrough such fragrance-emitting fibers.
Furthermore, U.S. Pat. No. 4,713,291 issued on Dec. 15, 1987 discloses fragrant fiber wherein a fragrant sheath-core composite fiber xe2x80x9csuitable for beddingxe2x80x9d and having a cross section including a sheath and a core including a hollow portion wherein an aromatic perfume having a boiling point higher than 150xc2x0 C. under normal pressure is incorporated and dispersed in an amount 0.1 to 10.0% by weight in a thermoplastic polymer constituting the core. The core component in U.S. Pat. No. 4,713,291 is preferably a polyethylene-type polymer, and the sheath component is preferably a polyethylene terephthalate polymer. One of the typical compositions of the aromatic perfume of U.S. Pat. No. 4,713,291 is an essential oil mixture including (i) 10 to 20% of lemon oil; (ii) 5 to 15% of bergamot oil; (iii) 2 to 8% of lavender oil; (iv) 2 to 8% of lemongrass oil; (v) 2 to 8% of cedarwood oil and (vi) 0.5 to 1.5% of jasmine absolute. The disclosure of U.S. Pat. No. 4,713,291 is incorporated by reference herein. However, U.S. Pat. No. 4,713,291 does not disclose the use of such fragranced fibers as an essential component of a dry wipe or a wet wipe. Antimicrobial component-containing fibers which can be sewn into textile prostheses for insertion into the body, and epidermal pads and bandages are disclosed in PCT Published Application No. 99/21507 published on May 6, 1999. However, PCT Published Application No. 99/21507 does not disclose the creation of fibers which can be used in conjunction with wet wipes or dry wipes and, furthermore, does not disclose the incorporation into such fibers of fragrance materials.
European Published Patent Application No. 930,488 published on Jan. 18, 1999 discloses a time-temperature indicator device comprising a polymeric layer with first and second surfaces and dye composition adhered to the first surface comprising a dye which diffuses into the polymeric layer due to the cumulative time-temperature exposure wherein the dye is invisible by visible radiation and is detectable as a result of absorption of non-visible radiation.
However, the use of such color-indicating systems in fragranced fibers in European Patent Application No. 930,488 or any other prior art is neither disclosed nor inferred.
The entire specifications of PCT Published Application No. 99/21507, European Published Patent Application No. 930,488 as well as U.S. Pat. Nos. 3,567,118 and 3,567,119 are incorporated by reference herein.
In summary, although the prior art shows fragranced fibers, nothing in the prior art sets forth the creation of such fibers which have unexpected properties which permit them to be used in wet wipes or dry wipes which are permanently and continuously fragrance-emitting and optionally antimicrobial substance-emitting.
Our invention is directed to fragrance-imparting component-emitting fiber which controllably and continuously releases fragrance and which optionally also releases antimicrobial agent and which optionally contains at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance, at least for the time period of use of an article into which the fiber is woven.
Thus, for example use of such fiber involves a permanently and continuously fragrance-emitting dry or wet wipe laminar fabric article comprising a non-woven fabric larmina having woven therethrough and substantially throughout at least a major portion of the lamina surface the continuous fragrance-containing thermoplastic substantially water-insoluble fiber of our invention which controllably and continuously releases fragrance (which may also have antimicrobial properties) at least for the time period during which the fabric article is in use. Optionally, one or more antimicrobial substances may also be releasably contained in the fiber containing the fragrance or in a fiber apart therefrom. Optionally, the fiber may also contain at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance. The fabric article useful in conjunction with our invention optionally contains additional fragrance and/or antimicrobial agent and/or color indicator absorbed or adsorbed on the non-woven fabric lamina.
Our invention is also directed to a process for creation of the fragrance-containing polymeric fiber which optionally also contains (i) at least one antimicrobial agent; and (ii) at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance.
More specifically, the process of our invention for producing a fragrance-emitting fiber comprises the sequential steps of:
(a) providing polymer matrix particles having releasably entrapped therein at least one aroma-imparting component which optionally has efficacious antimicrobial properties in a concentration of from about 1% up to about 45% by weight of the polymer particles and optionally (i) one or more antimicrobial substances and/or (ii) at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance (with the polymer matrix being composed of a thermoplastic substantially water-insoluble polymer);
(b) optionally admixing the matrix particles with a compatible thermoplastic substantially water-insoluble polymer whereby a matrix polymer mixture is formed; and
(c) forming the polymer particles or matrix polymer mixture into one or more continuous fragrance-imparting component-emitting fibers of from about 3 denier up to about 60 denier.
The polymer matrix particles having releasably entrapped therein at least one aroma-imparting component which optionally (i) has efficacious antimicrobial properties and/or (ii) has contained therein at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance may be prepared according to processes well known in the prior art, for example, the processes as set forth in U.S. Pat. No. 4,542,162 issued on Sep. 17, 1985, the specification for which is incorporated herein by reference. Furthermore, such polymer matrix particles having releasably entrapped therein at least one aroma-imparting component may also be prepared according to United Kingdom Patent Specification No. 1,589,201 assigned to Hercules, Inc., which discloses a thermoplastic resin body consisting of a thermoplastic polymer of ethylene and 6-60 weight percent of a polar vinyl monomer selected from the group consisting of vinyl acetate, methyl acrylate, ethyl acrylate; buytl acrylate and acrylic acid wherein the perfumed resin body is suitable for the preparation of shaped objects from which the perfume odor emanates over a prolonged period at a stable level. Another process for preparing the polymer matrix particles having releasably entrapped therein at least one aroma-imparting component is U.S. Pat. No. 3,505,432, the specification for which is incorporated by reference herein. U.S. Pat. No. 3,505,432 discloses a method of scenting a polyolefin and forming polyolefin-scented particles which comprises:
(a) mixing a first amount of liquid polyolefin, e.g., polyethylene or polypropylene, with a relatively large amount of scent-imparting material to form a flowable mass;
(b) forming drops from said mass and causing substantially instantaneous solidification of said drops into polyolefin pellets having a relatively large amount of scent-imparting material imprisoned therein;
(c) if desired, melting said pellets with a second amount of said polyolefin said second amount being larger than said first amount; and
(d) solidifying the melt of (c).
Other references which disclose microporous polymers useful in the practice of our invention are set forth as follows:
(a) U.S. Pat. No. 4,247,498 issued on Jan. 27, 1981, the specification for which is incorporated by reference herein;
(b) U.S. Pat. No. 4,156,067 issued on May 22, 1979, the specification for which is incorporated by reference herein; and
(c) U.S. Pat. No. 4,521,541 issued on Jun. 4, 1985, the specification for which is incorporated by reference herein.
The resulting polymer matrix particles having releasably entrapped therein at least one aroma-imparting component, may then be further admixed with additional compatible polymer. Thus, for example, additional polypropylene may be admixed with polypropylene particles which contain between about 1 and about 45% by weight of the polymer of fragrance.
Optionally, one or more compatible coloring materials or color-forming materials which are useful for ascertainment of the exhaustion or substantial reduction of fragrance may be included in the fiber. Such coloring materials are useful according to one of the following schemes:
(A) FIBER CONTAINS FRAGRANCE+LEUCO DYE;
↓xcex8A
(B) FRAGRANCE OIL MOLECULES DIFFUSE INTO ENVIRONMENT SURROUNDING FIBER, BUT LEUCO DYE DOES NOT DIFFUSE
↓xcex8B
(C) OXYGEN (IN AIR) THEN COUNTERDIFFUSES INTO FIBER AS A RESULT OF ABSENCE OF FRAGRANCE MOLECULES
↓xcex8C
(D) [O2+LEUCO DYExe2x86x92DYE]
or Scheme B:
(A) FIBER CONTAINS FRAGRANCE+BLEACHABLE DYE [BLEACHABLE VIA OXIDATION]
↓xcex8Axe2x80x2
(B) FRAGRANCE OIL MOLECULES DIFFUSE INTO ENVIRONMENT SURROUNDING FIBER. BUT DYE DOES NOT DIFFUSE;
↓xcex8Bxe2x80x2
(C) OXYGEN (IN AIR) THEN COUNTERDIFFUSES INTO FIBER AS A RESULT OF ABSENCE OF FRAGRANCE OIL MOLECULES,
↓xcex8Cxe2x80x2
(D) [O2+DYExe2x86x92LEUCO DYE]
In the aforementioned xe2x80x9cScheme A,xe2x80x9d the total time for the fragrance release xcex8A is large in comparison to the time needed for oxygen counterdiffusing into the fiber and reaction of said oxygen with the leuco dye to form the dye, thusly:
xcex94xcex8≅xcex8A; xcex8A greater than  greater than  greater than xcex8B+xcex8C;
and the total time is governed by the algorithm:   Δθ  =                    θ        A            +              θ        B            +              θ        C              =                            ∫                      F            1                                F            2                          ⁢                                            ∂              θ                                      ∂              F                                ⁢                      ⅆ            F                              +                        1                      k            ⁡                          [                              LD                _                            ]                                      ⁢                  ln          e                ⁢                                            (                              P                                  O                  2                                            )                        2                                              (                              P                                  O                  2                                            )                        1                              +                        ∫                                    (                              P                                  O                  2                                            )                        1                                              (                              P                                  O                  2                                            )                        2                          ⁢                              (                                          ∂                θ                                            ∂                                  P                                      O                    2                                                                        )                    ⁢                      ⅆ                          P                              O                2                                                        
wherein the reciprocal of the rate of fragrance release is shown by the symbol:       [                  ∂        F                    ∂        θ              ]        -    1  
which is equivalent to:   [            ∂      θ              ∂      F        ]
and the reciprocal of oxygen diffusion rate is shown by:       [                  ∂                  P                      O            2                                      ∂        θ              ]        -    1  
or       [                  ∂        θ                    ∂                  P                      O            2                                ]    .
The symbol: {overscore (L.D)} is the average concentration of leuco dye and the symbol: k is the reaction rate constant for the reaction of oxygen with leuco dye to form the dye.
Referring to xe2x80x9cScheme Bxe2x80x9d as set forth, supra, again the time of fragrance release is much greater than the time of oxygen counter diffusion into the fiber or reaction of oxygen with the dye in order to form a leuco dye, thusly:
xcex8Axe2x80x2 greater than  greater than  greater than xcex8Bxe2x80x2+xcex8Cxe2x80x2
wherein the symbol: xcex8Axe2x80x2 is the time for the fragrance to disappear; and the symbol: xcex8Bxe2x80x2 is the time for the oxygen counterdiffusion; and the symbol: xcex8Cxe2x80x2 is the time for reaction of the oxygen with the dye contained in the fiber to form a leuco dye (colorless). The aforementioned xe2x80x9cScheme Bxe2x80x9d is defined according to the algorithm:       Δθ    xe2x80x2    =                    θ        A        xe2x80x2            +              θ        B        xe2x80x2            +              θ        C        xe2x80x2              =                            ∫                      F            1                                F            2                          ⁢                              (                                          ∂                θ                                            ∂                F                                      )                    ⁢                      ⅆ            F                              +                        1                                    k              xe2x80x2                        ⁡                          [                              D                _                            ]                                      ⁢                  ln          e                ⁢                  xe2x80x83                ⁢                                            (                              P                                  O                  2                                            )                        2                                              (                              P                                  O                  1                                            )                        1                              +                        ∫                                    (                              P                                  O                  2                                            )                        1                                              (                              P                                  O                  2                                            )                        2                          ⁢                              (                                          ∂                θ                                            ∂                                  P                                      O                    2                                                                        )                    ⁢                      ⅆ                          P                              O                2                                                        
wherein the symbol: {overscore (D)} is the average concentration of dye and the symbol: kxe2x80x2 is the reaction rate constant for the reaction of oxygen with dye to form the leuco dye. The total amount of time taken for the entire scheme to be carried out is shown as:
xcex8Axe2x80x2+xcex8Bxe2x80x2+xcex8Cxe2x80x2.
Color materials and color-forming materials useful in the practice of this aspect of our invention are those set forth in Published European Application No. 932602-A2 published on Aug. 4, 1999, corresponding to PCT Application No. 99/03834-A2, the specification for which is incorporated by reference herein.
Materials which form colors on reaction with oxygen are specifically set forth in German Patent No. 29909427-U1 published on Jul. 22, 1999. Such a dye-forming system includes, for example (A) one or more specified 4,5-diamino-pyrazole derivatives such as 4-amino-5-dimethylamino-1-methyl-1H-pyrazole and (B) one or more couplers comprising 1,3-dihydroxybenzene; 1,3-diaminobenzene; or 3-aminophenol or their derivatives. The specification of German Patent No. 29909427-U1 published on Jul. 22, 1999 is incorporated herein by reference. In addition, polymeric colorance can be used in the practice of our invention, for example, those set forth specifically in Published European Application No. 93111-A1 published on Jul. 28, 1999, corresponding to PCT Application No. 98/10022, the specification for which is incorporated by reference herein. The corresponding U.S. PCT Application No. 1997 U.S. Pat. No. 906,642, the specification for which is incorporated by reference herein.
Furthermore, additional coloring systems that can be used in the practice of our invention are those set forth in U.S. Pat. No. 5,968,206 issued on Oct. 19, 1999, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,968,206 discloses compositions for oxidation dyeing comprising:
(a) at least one oxidation base of a para-phenylene diamene derivative; and
(b) 4-hydroxyindole as a coupler.
In addition, another system useful in the practice of our invention is that disclosed in U. Pat. No. 5,968,208 issued on Oct. 19, 1999, the specification for which is incorporated by reference herein. U.S. Pat. No. 5,968,208 is entitled: xe2x80x9cNEGATIVE DYES AND COLORATION PROCESS USING THEM.xe2x80x9d
The resulting mixture or the resulting polymer matrix particles having releasably entrapped therein at least one aroma-imparting component is then formulated into one or more continuous fragrance-imparting component-emitting fibers of from about 3 denier up to about 60 denier (1 denier means that 9,000 meters of fiber weigh 1 gram). The resulting mixtures can be formulated into such fibers by means of specific extruders for fiber manufacturing produced, for example, by the Davis-Standard Corporation of #1 Extrusion Drive, Pawcatuck, Conn. 06379. Such extrusion apparatus is preferably equipped with xe2x80x9chot runnerxe2x80x9d systems which enable the fibers to be produced at a uniformly constant diameter and to be produced in large quantity in an efficient manner.
In producing the fiber for purposes of weaving same into the lamina surface, it is preferred that the weight ratio of the polymer matrix particles having releasably entrapped therein at least one aroma-imparting component:additional compatible polymer being from about 2:1 down to about 1:1 with a preferred weight ratio of matrix particle:additional polymer being about 1.5:1.
The fibers of our invention which are used for weaving through the lamina surface need not necessarily be produced from matrix particles as set forth, supra. Instead, fragrance-emitting fibers for use in weaving same through the lamina surface of non-woven fabric may be produced according to processes as set forth in:
(a) PCT Application No. 99/21507 published on May 6, 1999;
(b) U.S. Pat. No. 4,713,291 issued on Dec. 15, 1987; and
(c) U.S. Pat. No. 3,567,118 issued on Mar. 2, 1971.
Each of the foregoing documents are incorporated herein by reference.
In PCT Application No. 99/21507, there is disclosed a synthetic fiber having cavities for holding large quantities of active material exemplified by medicaments. Fragrance materials can be introduced into such fibers in place of the disclosed medicaments. Thus, alternative processes for producing such fibers are as follows:
(i) manufacturing fibers by extruding a plural-component fiber from a spinneret, dissolving a soluble component to form cavities and securing a fragrance into the cavities;
(ii) manufacturing fibers by extruding a single component fiber from a spinneret forming cavities and introducing therein fragrance components; and
(iii) manufacturing fibers by mixing a fragrance with a polymer and extruding the resulting mixture from a spinneret and forming island-in-the-sea plural-component fibers.
In U.S. Pat. No. 4,713,291, a fragrant sheath core composite fiber having a cross section including a sheath and a core including a hollow portion is produced wherein an aromatic perfume having a boiling point higher than 150xc2x0 C. under normal pressure is incorporated and dispersed in an amount of from about 0.1 up to about 10.0% by weight in a thermoplastic polymer constituting the core. The core component is preferably a polyethylene-type polymer and the sheath component is preferably a polyethylene terephthalate polymer.
In U.S. Pat. No. 3,567;118, composite fiber materials are adapted for odorizing purposes by treating the fibrous material with a coating of a hydrophilic acrylate or methacrylate containing an appropriate essence. Entrapment of the essence can be prolonged by using a copolymer of the hydrophilic monomer with a minor amount of a hydrophobic monomer.
Fragrance materials which are preferably incorporated in the polymer matrix particles or which are, in general, incorporated into the fiber, which is to be woven through the lamina surface, are preferably those fragrances which also have antimicrobial properties; for example, those set forth in Published Japanese Application No.
JP101/94905 assigned to the Lion Corporation and published on Jul. 28, 1998, to wit:
(a) one or more aldehydes selected from cinnamic aldehyde, benzaldehyde, phenyl acetaldehyde, heptylaldehyde, octylaldehyde, decylaldehyde, undecylaldehyde, undecylenic aldehyde, dodecylaldehyde, tridecylaldehyde, methylnonyl aldehyde, didecylaldehyde, anisaldehyde, citronellal, citronellyloxyaldehyde, cyclamen aldehyde, xcex1-hexyl cinnamic aldehyde, hydroxycitronellal, xcex1-methyl cinnarnc aldehyde, methylnonyl acetaldehyde, propylphenyl aldehyde, citral, perilla aldehyde, tolylaldehyde, tolylacetaldehyde, cuminaldehyde, LILIAL(copyright), salicyl aldehyde, xcex1-amylcinnamic aldehyde and heliotropin; and
(b) from about 0.01 up to about 10 weight percent of one or more crystallization controlling agents selected from dibutyl hydroxytoluene, butyl hdroxyl anisole, propyl gallate, xcex1-tocopherol, isopropyl citrate, erysorbic acid, sodium erysorbate, guaiac resin, calcium disodium ethylenediamine tetra acetate and disodium ethylenediamine tetra acetate.
Other preferable fragrance compositions are those set forth in U.S. Pat. No. 5,420,104 issued on May 30, 1995, the specification for which is incorporated by reference herein. Such perfume compositions as described in U.S. Pat. No. 5,420,104 contain a cationic phospholipid having the structure: 
wherein R is linoleamidopropyl or cocamidopropyl; and X+y=3; a perfume base having antimicrobial activity and a fatty alcohol having from 10 up to 22 carbon atoms. Such a perfume base having antimicrobial activity contains:
benzyl acetate;
cyclohexyl acetate
styrallyl acetate;
n-octanol;
n-decanol;
amylcinnamic aldehyde
rosewood oil;
geraniol;
clove oil;
methyl jasmonate;
hydroxycitronellal;
methyl dihydrojasmonate;
ylang oil; and
mixture of methylionone isomers.
Furthermore, perfume compositions such as those set forth in:
U.S. Pat. No. 5,300,489 issued on Apr. 5, 1994 (the specification for which is incorporated by reference herein);
U.S. Pat. No. 5,932,771 issued on Aug. 3, 1999 (the specification for which is incorporated by reference herein); or
U.S. Pat. No. 5,942.272 issued on Aug. 24, 1999 (the specification for which is incorporated by reference herein),
may also be utilized in the fragrance-containing fiber which controllably and continually releases fragrance and which is woven through the major portion of the lamina surface of the non-woven fabric.
Thus, for example, the fragrance formulation contained in the fragrance-containing fiber which controllably and continuously releases fragrance, may include:
dihydromethyl jasmonic acid;
geraniol;
citronellol; and
oil of chamomile.
Along with the fragrances contained in the fragrance-containing fiber which controllably and continuously releases fragrances, the fiber may optionally have incorporated therein antimicrobial agents such as those set forth in the following list:
triclosan having the structure: 
xe2x80x83(an example is IRGASAN(copyright) DP 300, a trademark of Ciba Specialty Chermicals Holding Incorporated of Basel, Switzerland);
triclocarban having the structure: 
the compound having the structure: 
xe2x80x83marketed as AMICAL(copyright) by Angus Chemie GmbH of Zeppelinstrasse, Ibbenbuhren, Germany;
the compound having the structure: 
where X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl;
the compound having the structure: 
xe2x80x83a 2,3-dithiolane wherein R3 and R4 are the same or different hydrogen, halogen or alkyl, for example, the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
xe2x80x83wherein n is 0, 1 or 2;
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
the compound having the structure: 
xe2x80x83wherein the average values of x, y and z are, respectively, 75, 30 and 75;
compounds defined according to the structure: 
xe2x80x83wherein n is 1 or 2 and M is alkali metal when n is 1 or alkaline earth metal when n is 2; wherein R4 is hydrogen or methyl and R2 and R3 are hydrogen or C1-C18 alkyl as exemplified in Japanese Published Application JP111/16822, incorporated herein by reference; and
compounds defined according to the structure: 
xe2x80x83wherein R2 and R3 represent hydrogen, or C1-C18 alkyl and R4 is hydrogen or methyl (as exemplified in Japanese Published Application No. JP111/16822, incorporated herein by reference).
The fragrance-imparting component-emitting fiber or fibers of our invention may be woven through a non-woven fabric laminar substrate across at least a major portion of the surface area of a non-woven fabric laminar substrate by means of xe2x80x9cstitch bondingxe2x80x9d as more specifically described in such references as U.S. Pat. No. 5,902,757 issued on May 11, 1999, the specification for which is incorporated herein by reference, The quantity of fragrance material in the fragrance-containing fiber may vary from about 1% up to about 45% by weight of fragrance when no antimicrobial agent is present or the sum total of antimicrobial agent and fragrance may vary from about 1% up to about 45% by weight of the fiber when antimicrobial agent is present. Preferably, the amount of fragrance or sum total of fragrance and antimicrobial agent varies between about 1% and about 20% by weight of the fiber.
Thus, in summary, the process of our invention comprises more broadly the step of:
forming one or more continuous fragrance-imparting component-emitting fibers optionally containing (i) antimicrobial agent and/or (ii) at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance of from about 3 denier up to about 60 denier.
Also useful in the practice of our invention are the antimicrobial mixtures claimed in the following patents and published patent applications:
Japan Published Application No. 28/91622 granted on May 17, 1999 discloses and claims antibacterial agents which are mixtures of the compounds having the structures: 
wherein X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl:
Japan Published Application No. 28/91623 granted on May 17, 1999 discloses and claims a mixture of compounds having the structures: 
wherein X is halogen; Y is hydrogen or halogen; R1 is hydrogen or lower alkyl; R2 is hydrogen or hydrocarbyl; and R3 and R4 are the same or different hydrogen or halogen;
Japan Published Application No. 28/91629 granted on May 17, 1999 discloses the use as an antimicrobial mixture of the compounds having the structures: 
Japan Published Application No. 28/91635 granted on May 17, 1999 discloses the use as an antimicrobial mixture of the mixture of compounds having the structures: 
(wherein X is halogen; R1 is hydrogen, halogen or alkyl; R2 is hydrogen or alkyl; and R3 and R4 are the same or different hydrogen, halogen or alkyl); and the compound having the structure: 
European Published Application No. 917880 published on May 26, 1999 discloses an inclusion complex of the compound having the structure: 
with cyclodextrin derivatives.
Other polymers that can be used for creation of the continuous fragrance-containing fiber which controllably and continually releases fragrance at least for the time period during which the fabric article is in use are disclosed in PCT Application No. U.S. Ser. 99-05657 (PCT Ser. No. 97 93 86 14.1, the disclosure of which is incorporated by reference herein). PCT Application No. U.S. Ser. 99-05657 discloses the fragrance-emitting specially designed hydrophilic polyurethanes with certain hydrophobic components that retain aroma chemicals in the dry state and provide sustained fragrance release upon moisture exposure. The polymers are soluble in solvent mixtures ranging from 95:5 up to 20:80 weight:weight propylene glycol:water. In addition, they are also soluble in solvent mixtures of lower alcohols:water with similar ranges. Accordingly, the fibers of our invention used in wet wipes and dry wipes, which are composed of the polymers of PCT Application No. U.S. Ser. 99-05657, are not to be used within the scope of this invention with alcohol or propylene glycol.
In forming polymer matrix particles having releasably entrapped fragrances or fragrance components therein and optionally (i) one or more antimicrobial substances entrapped therein and/or (ii) at least one compatible coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance, the procedure of U.S. Pat. No. 4,542,162 granted on Sep. 17, 1985 may be utilized thusly:
Foamed fragrance-containing polymeric pellets are produced by means of introduction into a single screw or twin screw extruder of, in series, thermoplastic polymer followed by fragrance followed by the introduction of a gaseous blowing agent or blowing agent which will produce a gas which is inert to the polymer and to the fragrance fluid or solid previously introduced into the extruder. Antimicrobial agent and/or coloring or color-forming agent may optionally be introduced simultaneously with the introduction of fragrance or upstream from the point of introduction of fragrance into the extruder or downstream from the point of introduction of the fragrance into the extruder.
The advantages of using the foamed polymeric particles are multiple, to wit: improved handling; greater retention of fragrance; and, if desired, antimicrobial agent; greater length of time during which release of fragrance and, optionally (i) antimicrobial agent and/or (ii) coloring material or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance from polymer is at xe2x80x9csteady statexe2x80x9d or xe2x80x9czero order.xe2x80x9d
The nature of the extruder utilized in the process of our invention to form the foamed polymeric fragrance-containing polymer particles of our invention may be either single screw or double screw. Thus, the types of extruders that can be used are disclosed at pages 246-267 and 332-349 of the Modern Plastics Encyclopedia, 1982-1983, published by the McGraw-Hill Publishing Company, the disclosure of which is incorporated by reference herein. Similarly, such extruders are disclosed in the Modern Plastics Mid-November 1996 Encylcopedia, published by the McGraw-Hill Publishing Company, the disclosure of which is incorporated by reference herein. More specifically, examples of extruders which are usable in carrying out this aspect of the process of our invention are as follows:
1. The Welex xe2x80x9cSuper Twinchxe2x80x9d 3.5 inch extruder manufactured by Welex Incorporated, 850 Jolly Road, Blue Bell, Pa. 19422;
2. Krauss-Maffei twin screw extruder manufactured by the Krauss-Maffei Corporation/Extruder Division, 3629 West 30th Street South, Wichita, Kans. 67277;
3. Modified Sterling model 4000 and 5000 series extruder manufactured by Sterling Extruder Corporation of 901 Durham Avenue, South Plainfield N.J.;
4. CRT (xe2x80x9cCounter-Rotating Tangentialxe2x80x9d) Twin Screw Extruder manufactured by Welding Engineers, Inc. of King of Prussia, Pa. 19406;
5. The Leistritz Twin Screw Dispersion Compounder manufactured by the American Leistritz Extruder Corporation of 198 U.S. Route 206 South, Somerville, N.J. 08876;
6. The ZSK Twin Screw Co-Rotating Extruder manufactured by the Werner and Pfleiderer Corporation of 663 East Crescent Avenue, Ramsey, N.J. 07746;
7. The Farrel Extruder manufactured by Farrel Connecticut Division, Emhart Machinery Group, Ansonia, Conn. 06401;
8. The MPC/V Baker Perkins Twin Screw Extruder manufactured by the Baker Perkins Inc. Chemical Machinery Division of Saginaw, Mich. 48601; and
9. The Berstorff single screw, twin screw or foam extrusion equipment manufactured by the Berstorff Corporation, P.O. Box 240357, 8200-A Arrowridge Boulevard, Charlotte, N.C. 28224.
In producing the foamed fragrance-containing polymer particles useful in the practice of our invention (which optionally contain (i) antimicrobial agent and/or (ii) at least one compatible coloring or color-forming material which is useful for ascertainment of the exhaustion or substantial reduction of fragrance), various polymers may be utilized, for example, low density polyethylene, high density polyethylene, polypropylene, the copolymer of ethylene and vinyl acetate, and polyvinyl chloride. More specifically, the polymers used in the practice of our invention may be copolymers of ethylene and a polar vinyl monomer selected from:
(a) vinyl acetate;
(b) ethyl acrylate;
(c) methyl acrylate;
(d) butyl acrylate; and
(e) acrylic acid,
including the hydrolyzed copolymer of ethylene and vinyl acetate. Preferred copolymers are ethylene vinyl acetate with about 9 to 60% vinyl acetate and ethylene/ethyl acrylate with about 6 to 18% ethyl acrylate. As set forth, supra, other polymers which may be admixed with such materials include the polyurethane polymers of PCT Application No. PCT-U.S. Ser. 99-05657, incorporated herein by reference.
Resins of the type disclosed for use as copolymers are commercially available in the molding powder form. For example, ethylene vinyl acetate copolymers are marketed by the E.I. duPont de Nemours Company under the tradename xe2x80x9cELVAX(copyright)xe2x80x9d and by the Arco Polymer Division under the trademark xe2x80x9cDYLAND(copyright)xe2x80x9d and by the Exxon Corporation of Linden, N.J. under the trademark xe2x80x9cDEXXON(copyright).xe2x80x9d Ethylene/ethyl acrylate copolymers are marketed by the Union Carbide Corporation under the tradename xe2x80x9cEEA RESINS(copyright).xe2x80x9d
The polymer is added to the single screw or twin screw extruder at a feed rate in the range of from about 80 up to about 300 lbs per hour, while maintaining the temperature in the screw extruder between about 160 and about 240xc2x0 C. If the polymer or copolymer powder is added to the extruder at a reference xe2x80x9cbarrel segment,xe2x80x9d then the fragrance and, optionally, the antimicrobial agent is added to the extruder in solid or liquid form under pressure downstream from the addition point of the polymer at one or more xe2x80x9cbarrel segmentsxe2x80x9d 2-9.
Thus, this aspect of our invention provides a process for forming fragrance and optionally (i) antimicrobial and/or coloring or color-forming liquid or solid-containing foamed polymeric particles such as foamed polymeric pellets, which include a relatively high concentration of a material having at least the function of fragrancing and optionally the function of (i) imparting antimicrobial properties to the ultimately-produced fiber and/or (ii) imparting coloring or color-forming or color-bleaching properties to the ultimately-produced fiber whereby the exhaustion or substantial reduction of fragrance can be ascertained. The fragrance and optionally the antimicrobial agent and optionally the color-forming or color-imparting agent, in a fluid or solid form, are added at xe2x80x9cbarrel segmentsxe2x80x9d 2-9 of the single screw or twin screw extruder. Furthermore, the fragrance and optionally antimicrobial agent and/or color-forming or color-imparting agent added at xe2x80x9cbarrel segmentsxe2x80x9d 2-9 must be previously made to be compatible with the polymer added at xe2x80x9cbarrel segmentxe2x80x9d 1 of the single screw or twin screw extruder.
The use as to type and proportion of fragrance and optionally (i) antimicrobial agent and/or (ii) color-forming or coloring or color-disappearing agent is limited only by either (a) their solubility in the resin or mixture of resins used and/or (b) the volume ratio of microvoids in the polymer to the said polymer and/or (c) the solubility of the fragrance and optionally (i) antimicrobial agent and/or (ii) color-forming or coloring or color-disappearing agent in the polymer on solidification. The proportion of fragrance and optionally (i) antimicrobial agent and/or. (ii) color-forming or coloring or color-disappearing agent can in many instances go up to 45% by weight based on the total weight of fiber which is to ultimately be used in being woven across at least a major portion of the surface area of the non-woven fabric laminar substrate.
Thus, the proportion of fragrance and optionally (i) antimicrobial agent and/or (ii) coloring agent, color-forming agent or color-disappearing agent to the weight of resin body for formation of the fiber to be woven across the non-woven fabric lamina can vary from small but effective amounts on the order of about 1% of the weight of the resin body (that makes up the fiber) up to about 45% by weight of the resin body (that makes up the weight of the fiber). In general, it is preferred to use between about 1% up to about 30% based on the weight of the resin body of the fragrance taken alone or taken together with optional (i) antimicrobial agent and/or (ii) coloring agent, color-forming agent or color-disappearing agent. This is an optimum amount balancing the proportion of fragrance and optionally (i) antimicrobial agent and/or (ii) coloring agent, color-forming agent or color-disappearing agent in the product against the time period over which the article emits the fragrance and optionally the antimicrobial agent, and against the tendency of the fragrance and optionally (i) the antimicrobial agent and/or (ii) the coloring agent, the color-forming agent or the color-disappearing agent fluid or solid to xe2x80x9coil out.xe2x80x9d This xe2x80x9coiling outxe2x80x9d is avoided as a result of the use of foaming agent.